Surface Dilational Rheology Research Articles

Mechanism of sodium alginate synergistically improving foaming properties of pea protein isolate: Air/water interface microstructure and rheological properties

The synergistic effect of polysaccharides plays a crucial role in regulating the foaming properties of protein based aerated foods. In this study, the synergistic improvement mechanism of pea protein isolate (PPI)-sodium alginate (SA) composite on the foaming performance was determined through multi-component interaction, air/water interface adsorption behavior and foam properties. The results of interactions between PPI and SA indicated that SA and PPI could form smaller and more stable soluble composite through hydrogen bonding, hydrophobic interactions, and electrostatic interactions. The α-helix content of PPI significantly decreased, and PPI exhibited a more flexible secondary structure. In depth research on the air/water interfacial behavior and interfacial microstructure through adsorption kinetics, surface dilatational rheology and Lissajous plots indicated that the PPI-SA composite could accelerate the adsorption process, constructing a highly viscoelastic interface mainly based on elasticity. The results of foam properties showed soluble PPI-SA composite could prepare smaller and more dense foam with thicker and smoother interface film, which was beneficial to the foam stability. The results of small amplitude oscillatory shear and large amplitude oscillatory shear suggested that foam prepared by soluble PPI-SA composite showed stronger ability to resist deformation whether in linear or nonlinear viscoelastic region, revealing the good mechanical properties of these foam under extreme processing conditions and feasibility to improve the quality of aerated food. When the mass ratio of PPI/SA was 1:0.3, the foam properties was strongest. When the mass ratio of PPI/SA exceeded 1:0.3, insoluble substances appeared in the composite system, which was disadvantageous to foam properties and deformation resistance. Therefore, the complexation of PPI and SA was an effective way to improve the air/water interface and foaming properties of PPI, providing theoretical guidance for targeted regulation of the foaming properties of protein based aerated foods.

Mung bean protein colloid mixtures and their fractions - A novel and excellent foam stabiliser

Protein aggregates are known to enhance foam stability by either increasing the thin film viscosity or by blocking the lamellae of a foam. In this study, we produced a mung bean protein colloids mixture (MPCM) by heating protein coacervates that were formed by liquid-liquid phase separation. The functionality of MPCM was compared to a mildly purified mung bean protein extract (MIL). The MPCM showed extraordinary foaming properties, much better than MIL, with foamability of 324 % and a half-life time of 400 min. This work focused on elucidating the exact interface and foam stabilising mechanism of the MPCM by separating the colloids (COL) from the supernatant/continuous phase of the MPCM (SUP). Their interfacial properties were studied by performing surface dilatational rheology and microstructure analysis. Finally, foaming properties, such as foamability, foam stability, and air bubble size, were studied.It was found that the highest foam capacity was observed for the SUP fraction by generating stiffer interfaces. This fraction also contributed to the high foam stability of the MPCM. The COL fraction was found to form a viscoelastic thin film between air bubbles, thereby decreasing the drainage rate of the foam. In brief, SUP and COL fractions co-operate in the formation of highly stable MPCM foam, leading to a promising plant-derived candidate for producing stable foams in food products.

Dynamic properties of the layers of cupin-1.1 aggregates at the air/water interface

Spread layers of amorphous aggregates of the structural domain of plant protein vicilin, cupin-1.1, at the water – air interface were studied by the surface tensiometry, dilational surface rheology, Brewster angle and atomic force microscopy. The layer properties differed strongly from the results for the layers of previously studied proteins. The dependency of the dynamic elasticity of the layer on surface pressure had two local maxima with the second peak being four times higher than the first one. In the region of the first maximum the obtained results are similar to those for dispersions of polymer microgels with a hairy corona. At the beginning of surface compression separate threads of the corona are stretched along the surface and the surface elasticity increases. The further compression results in the formation of loops and tails leading to a decrease of the elasticity. The second local maximum of the dynamic surface elasticity is presumably caused by the interactions of the rigid cores of the aggregates leading finally to the formation of multilayer structures at high surface pressures. In this case, the surface elasticity starts to decrease as a result of the segment exchange between different layers at the interface.

Effect of cationic dendrimer on membrane mimetic systems in the form of monolayer and bilayer

Interactions between a zwitterionic phospholipid, 1, 2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) and four anionic phospholipids dihexadecyl phosphate (DHP), 1, 2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG), 1, 2-dipalmitoyl-sn-glycero-3-phosphate (DPP) and 1, 2-dipalmitoyl-sn-glycero-3-phospho ethanol (DPPEth) in combination with an additional amount of 30 mol% cholesterol were separately investigated at air-buffer interface through surface pressure (π) - area (A) measurements. π-A isotherm derived parameters revealed maximum negative deviation from ideality for the mixtures comprising 30 mol% anionic lipids. Besides the film functionality, structural changes of the monomolecular films at different surface pressures in the absence and presence of polyamidoamine (PAMAM, generation 4), a cationic dendrimer, were visualised through Brewster angle microscopy and fluorescence microscopic studies. Fluidity/rigidity of monolayers were assessed by surface dilatational rheology studies. Effect of PAMAM on the formation of adsorbed monolayer, due to bilayer disintegration of liposomes (DPPC:anionic lipids= 7:3 M/M, and 30 mol% cholesterol) were monitored by surface pressure (π) - time (t) isotherms. Bilayer disintegration kinetics were dependent on lipid head group and chain length, besides dendrimer concentration. Such studies are considered to be an in vitro cell membrane model where the alteration of molecular orientation play important roles in understanding the nature of interaction between the dendrimer and cell membrane. Liposome-dendrimer aggregates were nontoxic to breast cancer cell line as well as in doxorubicin treated MDA-MB-468 cell line suggesting their potential as drug delivery systems.

Improving the whey protein foam structures by using novel acetylated triglycerides: A response surface methodology (RSM) approach

AbstractProtein foams are common to foods, such as meringue, whipped cream and mousses. Stability is a challenging issue determined by fat and sugar content. We hypothesize that acetyl‐triacylglycerols (acetyl‐TAG) that possess sn‐3 acetate group with high oleic content can provide stability to the foam at reduced sugar concentrations by increasing the surface viscosity and minimizing serum drainage. A fractional factorial Box‐Wilson design was used to investigate the effects of whey protein concentration (WPI) (2–10 wt%), sucrose concentration (SC) (10–30 wt%) and acetyl‐TAG concentration (ATC) (0–1 wt%) on overrun (FO), stability against serum drainage (FD) and surface dilatational rheology. Each response was analyzed by linear regression model fitting and a backward elimination algorithm for significance (α = 0.01). FO was significantly affected (p < 0.01) by WPI and ATC, but not sucrose concentration. The optimum overrun (nearly 700%) was obtained at 9 wt% WPI and 0.6 wt% ATC. Drainage and viscoelastic properties were significantly (p < 0.01) affected by all process variables. Dynamic complex modulus (|E|) as measured using an optical tensiometer was around 30–40 mN/m when acetyl‐TAG was higher than 0.5 wt%. Our findings indicated that the acetyl‐TAG can be used to enhance the stability of protein foams in reduced sugar food products, however, not at high sugar concentrations (30 wt%).

Self-aggregation, dilational surface rheology and foaming properties of 1-O-dodecyl diglyceryl ether compared to n-dodecyl-β-D-maltoside and pentaethyleneglycol monododecyl ether

Diglyceryl alkyl esters are good foaming agents but the ester linker can be sensitive to pH, chemicals and temperature unlike the ether function. In this work, the foaming properties of a diglyceryl ether, namely 1-O-dodecyl diglyceryl ether (C12Gly2), are compared to those of n-dodecyl-β-D-maltoside (C12Glc2) and pentaethyleneglycol monododecyl ether (C12E5). The self-aggregation behaviour of C12Gly2 and adsorption at the air–water interface has been first investigated. For the three surfactants, the dynamic response of the interface, measured in oscillatory bubble interfacial rheology experiments below CMC, is compared and put in relation with their foaming properties. In particular, the foamability by air sparging at a concentration of 10 times the CMC, the foam stability over 1 h and the foam density are quantified.It is shown that C12Gly2 forms liquid crystals at low concentration (∼10CMC). C12E5, with a lower elasticity high frequency limit ε0, forms unstable foam with quick drainage and breakdown, whereas higher ε0 surfactants C12Gly2 and C12Glc 2 form much more stable foams, resulting from hydrogen bonds between the polar heads of C12Glc 2 and C12Gly2. Differences in C12Gly2 and C12Glc2 foams lay in initial bubble size (smaller for the C12Glc 2). In C12Gly2 foam, the main destabilization phenomenon is coalescence over drainage, and the foam volume only decreases by 30% in 1 h.

Dynamic interfacial properties and foam behavior of licorice root extract solutions

Licorice (Glycyrrhiza glabra) is a useful plant of the family Fabaceae, with sweet-tasting roots. The root extract of this plant is rich in saponins, so it can be considered a source of natural surfactants. This research provides some applicable information about the dynamic surface tension and foam behavior of aqueous solutions of licorice root extract (LRE). The pendant drop shape analysis was utilized to study the surface tension and dilational surface rheology of LRE at the water/air interface. The Bikerman type experiment was used to measure foamability and foam stability of aqueous LRE solutions. The equilibrium surface tensions reveal that the LRE contains surface-active components and is capable of reducing the surface tension by 25 mN/m at the critical aggregation concentration (CAC). The surface dilational visco-elasticity measurements proved that the adsorption layers are predominantly of elastic nature. Also the foamability and foam stability show a meaningful correlation with the dynamic surface properties. This study aims to contribute to the development of appropriate utilization of the benefits provided by a biosurfactant source in foam-related commercial applications.

Effect of deacetylation degree and molecular weight on surface properties of chitosan obtained from biowastes

A surface characterization of two types of unmodified chitosan properties with different molecular weight (MW) and deacetylation degree (DD) was carried out in terms of polymer concentration (a concentration lower than the saturation, the saturation concentration and a supersaturated concentration). The modification of the production conditions allowed to obtain chitosan samples with different properties (MW and DD), which eventually determined its surface activity. Thus, a kind of tailor-made chitosan may be designed to be adapted to different applications. Surface activity has been analysed by mean of measurements of surface tension, dilatational and shear rheology. The results have demonstrated that chitosan possessed a good surface activity at high ionic strength. Also, the increase in the concentration of chitosan in the solution, and the increase in molecular weight (and, therefore, a decrease in the degree of deacetylation) favoured the formation of aggregates, which improved the adsorption kinetics. The latter allowed adequate elasticity values to be reached more quickly. These properties are reached faster for the higher molecular weight chitosan (lower degree of deacetylation), due to the more hydrophobic character that facilitates the interactions between the adsorbed aggregates. Surface rheology revealed a predominantly elastic behaviour of chitosan film. All of these results strengthen the idea that chitosan behaves as a surface-active hydrophilic Pickering agent.

Foaming properties of the complex of chitooligosaccharides and bovine serum albumin and its application in angel cake

The complex of chitooligosaccharides (COS) and protein is worthy of investigation, as COS is an important functional ingredient and the functional properties of protein might be improved after complexation. Using bovine serum albumin (BSA) as the model protein, this work explored the foaming properties and interfacial behavior of COS-BSA complex, as well as its application as a substitute for egg whites in angel cake. The effects of pH and mixing ratio ( r ) on the foam properties and interfacial behavior of COS-BSA complex were studied using dilute solution. And the effects of the COS-BSA substitution rate on the physical properties and microbial storability of the cake were studied. Compared with BSA, the foaming capacity and foam stability of COS-BSA complexes were significantly improved in the pH range of 3.0–10.0, and both the foaming capacity and foam stability of COS-BSA complexes at pH 7.0 were in the order of r 0.5 ≥ r 0.25 ≥ r 1.0 > r 2.0 > BSA > COS. Angel cake with the COS-BSA substitution rate of 25% had the best physical properties, in which COS and BSA had a synergistic effect on the specific volume and texture of the cake. The substitute of COS-BSA complex for egg white in angel cake significantly inhibited microbial growth during storage. This work provided COS-BSA complex as a substitute for egg white in cake making, and COS-BSA complex improved the physical properties of cake and inhibited microbial growth. • Chitooligosaccharides improved foaming properties of bovine serum albumin. • Good foaming of complexes was related with their surface dilatational rheology. • Cake with complex substitution rate of 25% exhibited the best physical properties. • Complex addition in cake significantly inhibited microbial growth during storage.

Cruciferin versus napin – Air-water interface and foam stabilizing properties of rapeseed storage proteins

Rapeseed protein extract has high nutritional value and good techno-functionalities, e.g. in foam systems. Yet, its exact interface and foam stabilizing mechanisms are not well understood. Rapeseed proteins comprise mainly of cruciferin and napin. Our aim was to systematically investigate the interface stabilization behaviors of cruciferin, napin and combinations of both at air-water interfaces. We used surface (dilatational and shear) rheology and microstructure imaging (AFM) and linked their behavior to their foaming properties. We observed that napin adsorbed faster at the air-water interface than cruciferin due to its smaller size, leading to 90% higher foam overrun than cruciferin (320%). The interfaces showed distinct differences in structure and mechanical properties, as cruciferin formed stiff solid-like interfaces with Ed’ = 72.5 mN/m and Gi’ = 9.0·10−3 Pa m, leading to high foam stability (half-life time 220 min). Napin formed weaker less stretchable interfaces (Ed’ = 61.8 mN/m; Gi’ = 6.7·10−3 Pa m), leading to substantially lower foam stability (half-life time 23 min). Cruciferin and napin were also mixed at 3:1, 1:1 and 1:3 (w/w) ratios. Napin increased the foamability of all mixtures with foam overrun between 400 and 420%. The mixture at 3:1 cruciferin-to-napin ratio had comparable foam stability with pure cruciferin since cruciferin dominated the mechanical properties of the air-water interface. Higher napin contents largely decreased foam stability with half-life time decreasing to 80 min. These findings provide a comprehensive understanding of the behaviors of rapeseed proteins at air-water interfaces and their link to foaming properties, which can be used to tailor the properties of aerated products stabilized by rapeseed proteins.

DNA Penetration into a Lysozyme Layer at the Surface of Aqueous Solutions.

The interactions of DNA with lysozyme in the surface layer were studied by performing infrared reflection–absorption spectroscopy (IRRAS), ellipsometry, surface tensiometry, surface dilational rheology, and atomic force microscopy (AFM). A concentrated DNA solution was injected into an aqueous subphase underneath a spread lysozyme layer. While the optical properties of the surface layer changed fast after DNA injection, the dynamic dilational surface elasticity almost did not change, thereby indicating no continuous network formation of DNA/lysozyme complexes, unlike the case of DNA interactions with a monolayer of a cationic synthetic polyelectrolyte. A relatively fast increase in optical signals after a DNA injection under a lysozyme layer indicates that DNA penetration is controlled by diffusion. At low surface pressures, the AFM images show the formation of long strands in the surface layer. Increased surface compression does not lead to the formation of a network of DNA/lysozyme aggregates as in the case of a mixed layer of DNA and synthetic polyelectrolytes, but to the appearance of some folds and ridges in the layer. The formation of more disordered aggregates is presumably a consequence of weaker interactions of lysozyme with duplex DNA and the stabilization, at the same time, of loops of unpaired nucleotides at high local lysozyme concentrations in the surface layer.

Synergy in Aqueous Systems Containing Bioactive Ingredients of Natural Origin: Saponin/Pectin Mixtures.

Biocompatible and biodegradable ingredients of natural origin are widely used in the design of foam and emulsion systems with various technological applications in the food, cosmetics and pharmaceutical industries. The determination of the precise composition of aqueous solution formulations is a key issue for the achievement of environmentally-friendly disperse systems with controllable properties and reasonable stability. The present work is focused on the investigation of synergistic interactions in aqueous systems containing Quillaja saponins and Apple pectins. Profile analysis tensiometer (PAT-1) is applied to study the surface tension and surface dilational rheology of the adsorption layers at the air/solution interface. The properties and the foam films (drainage kinetics, film thickness, disjoining pressure isotherm, critical pressure of rupture) are investigated using the thin-liquid-film (TLF) microinterferometric method of Scheludko–Exerowa and the TLF-pressure-balance technique (TLF-PBT). The results demonstrate that the structure and stability performance of the complex aqueous solutions can be finely tuned by changing the ratio of the bioactive ingredients. The attained experimental data evidence that the most pronounced synergy effect is registered at a specific saponin:pectin ratio. The obtained information is essential for the further development of aqueous solution formulations intended to achieve stable foams based on mixtures of Quillaja saponins and Apple pectins in view of future industrial, pharmaceutical and biomedical applications.

Spread Layers of Lysozyme Microgel at Liquid Surface.

The spread layers of lysozyme (LYS) microgel particles were studied by surface dilational rheology, infrared reflection–absorption spectra, Brewster angle microscopy, atomic force microscopy, and scanning electron microscopy. It is shown that the properties of LYS microgel layers differ significantly from those of ß-lactoglobulin (BLG) microgel layers. In the latter case, the spread protein layer is mainly a monolayer, and the interactions between particles lead to the increase in the dynamic surface elasticity by up to 140 mN/m. In contrast, the dynamic elasticity of the LYS microgel layer does not exceed the values for pure protein layers. The compression isotherms also do not exhibit specific features of the layer collapse that are characteristic for the layers of BLG aggregates. LYS aggregates form trough three-dimensional clusters directly during the spreading process, and protein spherulites do not spread further along the interface. As a result, the liquid surface contains large, almost empty regions and some patches of high local concentration of the microgel particles.

Synergism between betaine surfactants under high-salt conditions

Foam properties and surface dilational rheology of single and mixed LHSB (lauramidopropyl hydroxyl sulfobetaine)-OAB (oleic amide propyl betaine) surfactants were measured to investigate the synergism between the two components. Experimental results showed obvious synergistic effects in foam stability, dilational modulus, and phase angle between LHSB and OAB. Moreover, interaction parameters were calculated to quantitatively characterize the synergism. The negative interaction parameters between LHSB and OAB demonstrated that there was an attractive interaction between LHSB and OAB, and the attractive interaction contributed to forming the dense surfactant layer at the liquid/air layer, which in turn improved foam stability. The negative values of parameters reached their maximum when the LHSB: OAB molar ratio ranged from 1:1 to 1:2, the same time the foam stability reached its maximum. The interaction between LHSB and OAB was confirmed by 2D NOSEY (two-dimensional nuclear overhauser enhancement spectroscopy) experiments, the interaction between LHSB and OAB could be attributed to the hydrogen bonding or the electrostatic interaction between the hydrophilic groups of the two surfactants.

The Effects of Cholesterol Oxidation on Erythrocyte Plasma Membranes: A Monolayer Study.

Cholesterol plays a key role in the molecular and mesoscopic organisation of lipid membranes and it is expected that changes in its molecular structure (e.g., through environmental factors such as oxidative stress) may affect adversely membrane properties and function. In this study, we present evidence that oxidation of cholesterol has significant effects on the mechanical properties, molecular and mesoscopic organisation and lipid–sterol interactions in condensed monolayers composed of the main species found in the inner leaflet of the erythrocyte membrane. Using a combination of experimental methods (static area compressibility, surface dilatational rheology, fluorescence microscopy, and surface sensitive X-ray techniques) and atomistic molecular dynamics simulations, we show that oxidation of cholesterol to 7-ketocholesterol leads to stiffening of the monolayer (under both static and dynamic conditions), significant changes in the monolayer microdomain organisation, disruption in the van der Waals, electrostatic and hydrophobic interactions between the sterol and the other lipid species, and the lipid membrane hydration. Surface sensitive X-ray techniques reveal that, whilst the molecular packing mode is not significantly affected by cholesterol oxidation in these condensed phases, there are subtle changes in membrane thickness and a significant decrease in the coherence length in monolayers containing 7-ketocholesterol.

Foam properties and interfacial behavior of the heteroprotein complex of type-A gelatin/sodium caseinate

Foam is one special colloid dispersion system and has been widely used in foods. This work aims to improve the foam properties of sodium caseinate (Cas) through the electrostatic complexation of Cas and type-A gelatin (GE), in which GE is one cheap and widely sourced basic protein. Turbidity and zeta potential measurements indicate that mass ratio (r = GE/Cas) was critical to the solubility of protein complexes at pH 6.0 and that soluble and insoluble complexes were respectively formed at low mass ratios (r = 0.25, 0.5 and 1) and high mass ratios (r = 2 and 4). All soluble and insoluble complexes exhibited better foaming capacity than that of Cas and GE, while only soluble complexes significantly improved the foam stability of Cas. Particularly, the foam half-time of GE/Cas mixture at r = 0.25 was 5525.2 ± 405.7 s and 2.1 times that of Cas. Surface dilatational rheology shows that the adsorption behavior of soluble and insoluble complexes was respectively similar to that of Cas and GE. Soluble complexes formed more viscoelastic interface films than Cas, which could explain the better foam stability of soluble complexes. Transmission electron microscopy shows that electrostatic complexation of GE/Cas destroyed the micelle structure of Cas to varying degree but produced new networks. GE/Cas heteroprotein complexes have the potential to be used as excellent foaming agents in food industry.

β-lactoglobulin microgel layers at the surface of aqueous solutions

The spread and adsorbed layers of β-lactoglobulin (BLG) microgel were investigated by the dilational surface rheology, atomic force microscopy and optical microscopy. It is shown that only careful purification of the BLG microgel dispersion gives a possibility to observe distinctions between the properties of spread layers of BLG nano- and micro particles on the one hand, and the properties the layers of BLG molecules on the other hand. The BLG particles do not have a thick and soft corona like poly(N-isopropylacryl) microgel. The fluctuations of the surface pressure of the BLG microgel layers at high surface compressions are a consequence of a special collapse mechanism, which has not observed earlier for the layers of both soft and rigid nano- and microparticles.

Effect of electrolyte on the surface dilational rheological properties of branched cationic surfactant

The studies of surface dilational rheology are important to detent the nature of adsorption film and the properties of foam. In this paper, the adsorption and dilational rheological properties of branched cationic surfactant hexadecanol polyoxyethylene(3) glycidyl ether ammonium chloride (C16G(EO)3PC) at the air-water interface in the absence and presence of electrolyte (NaCl) were investigated by drop shape analysis. The results show that the surface adsorption layer of C16G(EO)3PC behaves elastic in nature with high value up to 90 mN/m, which indicates that the slow relaxation process plays a main role because of the re-arrangement of long branched alkyl chain. The addition of NaCl will enhance diffusion-exchange process and accelerate the formation of film and decreases dilational elasticity obviously. At low NaCl concentration, the in-film slow relaxation process dominates the nature of film, dilational viscosity decreases with an increase of oscillating frequency. By adding more NaCl, diffusion-exchange process plays the crucial role and dilational viscosity increase as a function of frequency. Moreover, viscosity at high NaCl concentration shows larger value under higher oscillating frequency, indicating the contributions of fast diffusion-exchange process. The elastic adsorption film becomes to be viscoelastic by adding electrolyte.

Composition, functionality and structural correlates of mixed lipid monolayers at air-water interface

Physicochemical properties of lipid monolayer depend on its composition where a blend of lipids exhibit superior behaviour than the individual component. Surface pressure ( π ) – area ( A ) isotherms of mixed monolayer (PC mix ) formed by dipalmitoylphosphatidylcholine (DPPC), palmitoleylphosphatidylcholine (POPC), soyphosphatidylcholine (SPC) and hydrogenated soy phosphatidylcholine (HSPC) in combination with 30 mole % cholesterol (Chol) were obtained by using Langmuir trough. Effects of dipalmitoylphosphatidyethanolamine (DPPE) on its mutual miscibility at the air-water interface with DPPC ​+ ​Chol, POPC ​+ ​Chol, HSPC ​+ ​Chol and SPC ​+ ​Chol were also investigated separately, followed by studying the effects of DPPE and dipalmitoylphosphatidylglycerol (DPPG) to PC mix ​+ ​Chol and PC mix ​+ ​DPPE ​+ ​Chol respectively. Lift-off area, minimum molecular area, excess molecular area, collapse pressure, Gibbs free energy of interfacial mixing, compressibility modulii values were evaluated by analyzing the isotherms. Deviations from the ideal mixing behaviours were dependent on the composition of the lipid blends. Surface dilatational rheology studies could assess monolayer elasticity, whereas the film morphologies were analysed by Brewster angle microscopic (BAM) studies. DPPC induced formation of condensed monolayer, whereas film rigidity was increased with the incorporation of DPPE and DPPG into mixed systems. Interactions among the lipid components of the investigated mixed systems were thoroughly discussed from the point of view of polar head and acyl chain saturation and obtained results follow the sequence: PC mix ​+ ​DPPE ​+ ​DPPG ​+ ​Chol ​> ​PC mix ​+ ​DPPE ​+ ​Chol ​> ​individual PC ​+ ​DPPE ​+ ​Chol which could be translated into the bilayer studies. Such investigation of mixed lipid is important for class of its own composition and combined results are expected to contribute in better understanding the interaction of selected lipid in proposed blend.

PH effects on the molecular structure and charging state of β-Escin biosurfactants at the air-water interface

Saponins like β-escin exhibit an unusually high surface activity paired with a remarkable surface rheology which makes them as biosurfactants highly interesting for applications in soft matter colloids and at interfaces. We have applied vibrational sum-frequency generation (SFG) to study β-escin adsorption layers at the air-water interface as a function of electrolyte pH and compare the results from SFG spectroscopy to complementary experiments that have addressed the surface tension and the surface dilational rheology. SFG spectra of β-escin modified air-water interfaces demonstrate that the SFG intensity of OH stretching vibrations from interfacial water molecules is a function of pH and dramatically increases when the pH is increased from acidic to basic conditions and reaches a plateau at a solution pH of > 6. These changes are attributable to the interfacial charging state and to the deprotonation of the carboxylic acid group of β-escin. Thus, the change in OH intensity provides qualitative information on the degree of protonation of this group at the air-water interface. At pH < 4 the air-water interface is dominated by the charge neutral form of β-escin, while at pH > 6 its carboxylic acid group is fully deprotonated and, consequently, the interface is highly charged. These observations are corroborated by the change in equilibrium surface tension which is qualitatively similar to the change in OH intensity as seen in the SFG spectra. Further, once the surface layer is charge neutral, the surface elasticity drastically increases. This can be attributed to a change in prevailing intermolecular interactions that change from dominating repulsive electrostatic interactions at high pH, to dominating attractive interactions, such as hydrophobic and dispersive interactions, as well as, hydrogen bonding at low pH values. In addition to the clear changes in OH intensity from interfacial H2O, the SFG spectra exhibit drastic changes in the CH bands from interfacial β-escin which we relate to differences in the net molecular orientation. This orientation change is driven by tighter packing of β-escin adsorption layers when the β-escin moiety is in its charge neutral form (pH < 4).